Field of invention:
The present invention relates to the field of agrochemicals. The invention in particular relates to fungicidal combination, process for control of fungal pests in agricultural crops.
Background of the invention:
India is one of the largest producers of rice, accounting for 20% of all the world rice production. Rice is considered to be India's pre-eminent crop also being the staple food of the people in major parts of the country. Thousands of high yielding varieties have been developed for rice with the view to increase its production. The rice crop yield depends on many factors like variety, soil type, cultivation method and farm management practices.
Basically, rice crop requires hot and humid climatic conditions where the chances of infestation by fungus also may be high. Sheath blight disease of rice has been reported as a major limiting factor in successful rice cultivation in certain areas in India. The disease is caused by the fungus Rhizoctonia solani. Infected leaves senesce or dry out and die more rapidly, young tillers can also be destroyed which significantly reduces the leaf area of the canopy. Reduction in leaf area, along with the diseased-induced senescence of leaves and young infected tillers are the primary causes of yield reduction of the crop.
Few prior arts disclose certain pesticidal compositions comprising fungicidal active ingredient. For instance, US3723618A discloses a Fungicidal compositions in the form of synergistic combinations of 4, 5, 6, 7-tetrachlorophthalide and 0-(ethyl, n-propyl or isopropyl)-S, S-diphenylphosphorodithiolate which are individually known compounds, which combinations possess synergistic fungicidal properties especially for the control of diseases of rice plants.
US3663704A discloses an Agricultural fungicide and bactericide, a process for the preparation of same and a process for controlling rice blast.

None of the prior art documents therefore disclose a combination comprising the present invention provides a unique synergistic combination of a fungicide which provides excellent control of sheath blight disease in rice crop.
Object of the invention
An object of the present invention is to provide synergistic fungicidal combination that provides a control effect on fungal pest in agricultural crops
Summary of the invention
In accordance with the above objectives, the present invention provides a fungicidal combination comprising a fungicidally effective amount of Validamycin and Propiconazole useful in combating fungal infection and exhibit remarkable fungicidal activities against pathogenic fungi such as Rhizoctonia solani.
Accordingly, in one aspect the present invention provides a stable, synergistic fungicidal combination comprising Validamycin and Propiconazole in fungicidally effective amount.
Thus, in an embodiment, the combination of the present invention comprises about 2.8% by weight of Validamycin and 6% by weight of Propiconazole.
Detailed description of the invention:
Those skilled in the art will be aware that the invention described herein is subject to variations and modifications other than those specifically described. It is to be understood that the invention described herein includes all such variations and modifications. The invention also includes all such steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations of any two or more of said steps or features.
The present invention relates to a fungicidal combination comprising Validamycin and Propiconazole in agriculturally effective amount for controlling sheath blight disease in paddy crop.

The present invention discloses a synergistic fungicidal combination wherein said combination comprises:
(a) At least one fungicide belonging to the group of antibiotic fungicide.
(b) At least one fungicide belonging to the group of triazole fungicide.
(c) Excipients
The fungicidal active ingredients of the present invention may be selected from a group comprising antibiotic fungicides including but not limited to nystatin, levorin, trichomycin, amphotericin B, mikogeptin, Validamycin and griseofulvin. Preferably the antibiotic fungicide active ingredients are Validamycin.
Validamycin
[CAS no. 37248-47-8]
Molecular formula: C20H35NO13
A well-known antibiotic with fungi static activity in the form of colorless, odorless and hygroscopic powder. It is soluble in dimethylformamide, dimethyl sulphoxide, methanol; sparingly soluble in acetone, ethanol. It is produced by fermentation of Streptomyces hygroscopicus. It is an inhibitor of trehalase, an enzyme which mediates the digestion of the carbohydrate Trehalose and transport of glucose to the hyphal tips. It is a non-systemic antibiotic that causes abnormal branching of the tips of the pathogen, followed by cessation of further development. Being curative in action, Validamycin helps to control disease very fast.
The fungicidal active ingredients of the present invention may be selected from a group comprising Triazole fungicides including but not limited to azaconazole,

cyproconazole, bromuconazole, etaconazole, difenoconazole, epoxiconazole, hexaconazole, ipconazole, metconazole, propiconazole, prothioconazole, quinconazole, tebuconazole, tetraconazole, uniconazole, triticonazole, preferably the compound is propiconazole. Propiconazole
[CAS no. 60207-90-1]
IUPAC name: 1- [[2-(2, 4-dichlorophenyl)-4-propyl-l, 3-dioxolan-2-yl] methyl]-l,
2, 4-triazole has the following structure:
Molecular formula: C15 H17 Cb N3 O2
Propiconazole, first developed in 1979 by Janssen Pharmaceutical. Technical form is a yellowish, odorless viscous liquid that is completely miscible with ethanol, acetone, toluene and n-octanol (25°C). It is a triazole fungicide with a broad range of activity. It acts as a sterol demethylation inhibitor and inhibits the 14-a demethylase enzyme from demethylating a precursor to ergosterol. Without this demethylation step, the ergosterols are not incorporated into the growing fungal cell membranes and cellular growth is halted.
It is a systemic foliar fungicide and is used agriculturally on turf grasses grown for seed and aesthetic or athletic value, wheat, mushrooms, corn, wildrice, peanuts, almonds, sorghum, oats, pecans, apricots, peaches, nectarines, plu ms, banana, stone fruit, lemons and others. It has protective and curative action with acropetal translocation in the xylem.

It is stated that the presently disclosed synergistic fungicidal composition is expected to possess numerous advantages over the existing fungicidal compositions. It is expected to efficiently control sheath blight disease in paddy without any phytotoxic effects and is set to become a boon for Indian farmers.
In an embodiment, the present invention discloses a pesticidal combination comprising at least two fungicidal active ingredients.
The fungicidal combination of the present invention preferably comprises:
(a) Validamycin in the range of 1-5%, w/w of the total weight, preferably 1-4.5% w/w of the total weight of the combination.
(b) Propiconazole in the range of 1-20%, w/w of the total weight, preferably 1-18%) w/w of the total weight of the combination.
In another embodiment, the present invention discloses a composition comprising the combination of the present invention along with agriculturally acceptable excipients selected from the group comprising suspension concentrates (SC), emulsion, oil in water emulsion (EW), water dispersible granules (WG), wettable powder (WP), oil dispersion (OD), Microemulsion (ME) or Suspoemulsion (SE) and aqueous solutions.
The composition of the present invention may be any suitable compositions such as wet dispersible granules, emulsion, oil in water emulsion, wettable dispersible granules, wettable powder, preferably oil in water emulsion.
An inactive excipient is selected from the group consisting of dispersing agent, anti-freezing agent, emulsifier, wetting agent, defoamer or anti-foam agent, biocide, surfactant and filler.
The oil in water emulsion of the present invention comprises an anti- freezing agent, dispersing agent, wetting agent, a thickener, biocide, demineralized water, Defoamer and an antibacterial agent.
The present composition comprises one or more anti-freeze agent selected from the group comprising ethylene glycol, propylene glycol or glycerol, di-ethylene glycol (DEG), mono- ethylene glycol, di-ethylene glycol (DEG). The anti-freezing agent

may be present in an amount ranging from 3-7%, w/w preferably, the amount of anti-freezing agent is 4%, w/w of the composition.
The surfactant may be selected from the group comprising anionic/ non-ionic surfactants emulsifier (blend of sulphonated and ethoxylated hydrocarbons). Preferably the surfactant is blend of sulphonated and ethoxylated hydrocarbons. The said surfactant agent may be present in an amount ranging from 8-12%, w/w of the composition, preferably, the amount of surfactant is 10.00%), w/w of the composition.
The antifoaming agent may be selected from the group comprising silicone and silica, polydimethylsilioxan emulsion. Preferably the antifoaming agent is silicone. The said anti foaming agent may be present in an amount ranging from 0.2-1%%, w/w of the composition, preferably, the amount of antifoaming is 00.50%), w/w of the composition.
The Biocide/antibacterial agent may be selected from the group comprising formaldeldehyde, proxelgxl, 1-2 -benzisophiazolin-3-formaldehyde, griseofulvin, and amphotericin. Preferably the Biocide is formaldehyde. The said anti-bacterial agent may be present in an amount ranging from 0.2-1%%, w/w of the composition, preferably, the amount of antifoaming is 00.60%), w/w of the composition.
In another embodiment the present invention disclosed a process of preparing an emulsion oil water of the present invention.
1) Validamycin technical is dissolved in water to obtain an aqueous solution;
2) Anti-freezing agent, emulsifier propiconazole, solvent, defoamer sequentially added to obtain solution;
3) The aqueous solution of step (i) is added to solution of step (ii) preferably
with a stirring at the range of 500 rpm to 1500 rpm for 30 minutes.
It has been observed that the combination of the present invention possesses enhanced agricultural effect. Also the composition is synergistic and as an oil en water emulsion exhibits good activity

In another embodiment of the fungicidal combination and composition of the present invention discloses an effective control of sheath blight disease and also enhances the vigor/yield of the plant.
Rice sheath blight (ShB), caused by Rhizoctonia solani Kuhn is a destructive disease worldwide that causes significant yield loss and quality degradation. The lesions caused by Rhizoctonia solani are usually observed on the rice leaf sheaths, although leaf blades may also be affected. The initial lesions are small, ellipsoid or ovoid, and greenish gray and usually develop near the water line in lowland fields. Under favorable conditions, they enlarge and may coalesce, forming bigger, irregularly shaped lesions with grayish white centers and dark brown borders. The presence of several large spots on a leaf sheath usually causes the death of the whole leaf.
Advantage of one or more embodiments of the present invention:
1) The present invention provides a combination of Validamycin + Propiconazole at a synergistic ratio.
2) The composition comprising the combination is envoi mental safe, polluted free and showed no phtotoxicity to crops.
EXAMPLES:
The examples below are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Example 1 (a): Preparation of the combination of present invention
The present combination was prepared in the form of an oil in water emulsion by undertaking the following steps:
1) Validamycin technical is dissolved in water to obtain an aqueous solution;
2) Anti-freezing agent, emulsifier propiconazole, solvent, defoamer sequentially added to obtain solution;
3) The aqueous solution of step (i) is added to solution of step (ii) preferably
with a stirring at the range of 500 rpm to 1500 for 15 minutes to 45 minutes.

Table 1: Composition of CCP-2806 (Validamycin 2.8% + Propiconazole 6%) EW
Example 1 (b): Preparation of the combination of present invention
The present combination was prepared in the form of wettable dispersible granule (WDG) by undertaking the following steps:
1) All the raw materials such as wetting agent, dispersing agent, filler and technical's were mixed in the given proportion.
2) The above mass was mixed in blender and ground by jet mill.
3) Grinding was carried out until a mean particle size of below 10 microns was obtained.
4) After grinding, the resultant mix was mixed homogenously using blender and dough was prepared by dough mixer and granules were prepared through the extruder.
5) Granules as prepared above were dried using hot air or oven
6) Quality parameters of the final dry granules were checked

Table 2: Composition of CCP-2806 (Validamycin2.8% + Propiconazole 6%
WPG)
Table 3: Test parameters
Example 1 (c): Preparation of the combination of present invention
The present combination was prepared in the form of a wettable powder by undertaking the following steps:
1) All raw materials such as wetting agent, dispersant, dispersing agent, silica, china clay and Validamycin technical were mixed in the given proportion.

2) The above mass was mixed with blender and ground in jet mill.
3) Grinding was carried out until a mean particle size of below 10 microns was obtained.
4) After grinding, the resultant mix was mixed homogenously by blender followed by addition of propiconazole technical and mixed to obtain a homogenous mass.
5) Quality parameters of the final mix were checked.
Table 4: Composition of CCP-2806 (Validamycin2.8%+ Propiconazole 6% WP)
Table 5: Test parameters

Example 2: Bioefficacy tests of the present combination:
The bioefficacy of the present fungicidal combination was tested against the Rhizoctonia solani. in rice crop. The field trials were conducted during the Kharif season (2017-18) in karnal, Haryana of India. The trials were conducted in random block design (RBD) in a plot size of 60 x 5 m at a temperature of 30.2°C and at a relative humidity of 80%. A total of seven treatments in three replications were performed following the 1st application 30-25 days after transplanting and repeated at 10-15 days intervals. Total 2 applications were given.
Measured quantity of the chemical was added to the required volume of water @150 lit. /ac for spraying. The spray tank was filled with half the quantity of clean required volume of water and then the measured chemical (according to the dose) was added followed by the rest half quantity of water. The solution was stirred well and thorough coverage were ensured.
Table 6: below provides the treatment details of the trials conducted on rice with
the present formulation
Note CCP-2806 EW (Validamycin 2.8% + Propiconazole 06% EW)
Example 2(a): Evaluation of bioefficacy:
1): Target fungal pest: Sheath blight Disease in rice
Observations were taken on the incidence of Sheath disease before spray, 10 & 20 days after application. Disease assessment was done as per rating scale of 0 to 9 under given.

0 No visible symptoms
1 < 1% 3 1-10% 5 11-25% 7 26-50% 9 > 50%
Sum of all the numerical disease rating X 100
Percent Disease Index =
(PDI) Total No. of Hills (10) X Maximum disease grade in scale
(9)
Based on the PDI the per cent control of the disease was calculated based on the following formula
C-T
Percent disease control = x 100
C
Where C = Percent disease incidence (PDI) in Untreated/Control plot T = Percent disease incidence (PDI) in Treated plot
Example 2(b) Evaluation of Phytotoxicity
Visual observations were recorded at 3, 7 and 10 days after application. The parameters observed were leaf injury on tip/surface, necrosis, vein clearing, epinasty, hyponasty and wilting. For the rating on phytotoxicity the core scale of 1 - 10 was followed for leaf injury on tips/surface.

Table 7: Phytotoxicity symptoms scoring and rating for leaf injury on
tip/surface

Table 8: Effect of fungicidal treatments on sheath blight disease in Rice
Table 9: Phytotoxic effect of various treatments on Rice crop after 3 DAA
DAA - Days after application,
L- Leaf injury on tips/surface, N- Necrosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W-Wilting

Table 10: Phytotoxic effect of various treatments on Rice crop after 5 DAA
DAA - Days after application,
L- Leaf injury on tips/surface, N- Necrosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W- Wilting
Table 11: Phytotoxic effect of various treatments on Rice crop after 7 DAA
DAA - Days after application,
L- Leaf injury on tips/surface, N-Necrosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W- Wilting

Table 12: Phytotoxic effect of various treatments on Rice crop after 10 DAA
DAA - Days after application,
L- Leaf injury on tips/surface, N- Necrosis, V- Vein clearing, E- Epinasty, H- Hyponasty, W - Wilting

Result & conclusion:
Table 8 showed that maximum percent control of sheath blight disease was observed 92.57% and 93.19% with application of novel fungicide CCP-2806 EW at the dosage of 700 ml and 800 ml per acre of 20 days after 2nd application.
Further Table 9, 10, 11 and 12 no phytotoxicity was observed in all treatments on 3, 5, 7 and 10 days after application in paddy.
Application of novel fungicide CCP-2806 EW (Validamycin 2.8% + Propiconazole 6% EW) at the dosage of 700-800 ml per acre was observed to provide maximum percent control of Rhizoctonia solani caused by sheath blight disease on rice without any phytotoxicity on paddy rice.

CLAIM:
1) A synergistic fungicidal combination comprising an antibiotic fungicide and a triazole fungicide.
2) The synergistic fungicidal combination as claimed in claim 1, wherein the antibiotic fungicide is selected from the group consisting of nystatin, levorin, trichomycin, amphotericin B, mikogeptin, Validamycin and griseofulvin, preferably the antibiotic fungicide is Validamycin.
3) The synergistic fungicidal combination as claimed in claim 1, wherein the triazole is selected from the group consisting of azaconazole, bromuconazole, etaconazole, tebuconazole, propiconazole, ipconazole, hexaconazole, difenoconazole, Preferably propiconazole.
4) The synergistic fungicidal combination as claimed in claims 2 and 3, wherein Validamycin is present in an amount in the range from 1-5% w/w, preferably 1-4.5% w/w of the total weight of the combination and Propiconazole is present in an amount in the range from 1-20% w/w, preferably 1-18% w/w of the total weight of the combination.
5) A composition comprising the combination as claimed in claim 1 along with excipients.
6) The composition as claimed in claim 5, wherein the composition is selected from the group comprising suspension concentrate (SC), oil in water emulsion (EW), water dispersible granules (WG), wettable powder (WP), oil dispersion (OD), Microemulsion (ME) or Suspoemulsion (SE), preferably as an oil in water emulsion (EW).
7) The composition as claimed in claim 5, wherein inactive excipients are selected from the group consisting of dispersing agent, anti-freezing agent, emulsifier, wetting agent, defoamer or anti-foam agent, biocide, surfactant and filler.

8) The composition as in claim 7, wherein the anti - freezing agent is selected from the group consisting of propylene glycol, di-ethylene glycol (DEG), mono- ethylene glycol, di-ethylene glycol (DEG).
9) The composition as in claim 7, wherein the emulsifier is selected from the group consisting of consisting of anionic/ non-ionic surfactants (blend of sulphonated and ethoxylated hydrocarbons).
10) The composition as in claim 7, wherein the defoamer or anti- foaming agent is silicon or silica.
11) The composition as in claim 7, wherein the biocide is selected from group comprising Formaldehyde, proxelgxl, 1-2 -benzisophiazolin-3-formaldehyde.
12) A process of preparing the synergistic fungicidal combination as claimed in any of the preceding claims, wherein said process comprises the following steps:

1) Validamycin technical is dissolved in water to obtain an aqueous solution;
2) Anti-freezing agent, emulsifier, propiconazole, solvent, defoamer, are sequentially added to obtain solution;
3) The aqueous solution of step (i) is added to solution of step (ii) preferably with a
stirring at the range of 500 rpm to 1500 rpm for 15 minutes to 45 minutes.
13) The synergistic fungicidal combination as claimed in any of the preceding claims,
wherein the said combination is effective in controlling sheath blight disease in rice.